Method of treating asphaltic oils



'P. PHuTzMAN AND AG. L. GOODWIN.

METHOD 0F TREATING ASPHALVTIC OILS.

APPLICATION FILED SEPT. 27, 191.?.

Patented Dec. 13, 1921.

- 1N V ENTORS.

BY "9. d@ '5ML/Vb WITNESS:

A TTOR NE YS.

UNITED STATES PATENT OFFICE.

PAUL PRUTZMAN AND GUY L. GOODWIN, OF SANTA MARIA, CALIFORNIA, .ASSIGNORSBY MESNE ASSIGNMENTS, TO GENERAL PETROLEUM CORPORATION, A CORPORA- TIONOF CALIFORNIA.

METHOD OF TREATING ASPHALTIC OILS.

vSpecification of Letters Patent.

Patented Dec. 13, 1921.

Application led September 27,1917. Serial No. 193,420.

To all whom t may concern Be it known that We, PAUL PnUTzMAN and GUY L.GOODWIN, citizens of the United States, residing at Santa 'Marizu in thecounty of Santa Barbara and State of California, have inventedcertainvnew and uscful Improvements in Methods of Treating AsphalticOils, of which the following is a specification.

The hereinafter described invention relates to a method adapted moreparticularly for the treatment of the California asphaltic liquids, suchas petroleum. although, its use is not restricted or limited to thetreatment of asphaltic oils obtained in the State of California, and thesame is a method of producing a single fractionation without withoutheat decomposition, which decomposition usually results from the presentmethods employed for the treatment of such asphaltic oils, and thecommercial products which suffer most depreciation in value from' suchdecomposition` are lubricating oils, road oils and asphalts; the presentinvention being more particularly applicable for the manufacture orproduction of the three mentioned products of the asphaltic oils,although the invention is not limited to the roduction of suchmaterials, but provi es a cheap and desirable means for accomplishing areduction or a single fractionation of any mixture of hydrocarbons,excluding only such as have an appreciable vapor pressure at normaltemperatures, although, the invention may of course be applied to suchmaterials as contain a moderate proportion of volatiles, by firstremoving such, by other means of distillation.

The basic or underlying principle of the present invention, is, thetreatment of the hydrocarbon liquids by the passage or flow of hotcombustion products over the exposed surface of a sheet, film or mass ofthe asphaltic material to be fractionated, Whereby the followingimportant desiderata are gained, viz: a high degree of fuel economy, dueto the exceptionally favorable heat cycle; avoidance of decomposition,due to the low temperature and time factors fol-A lowing from the use ofa large relative vol- Amaintain the flow of liquid, and, in this case,

the process is single fractioning, as the vapor is removed in one. cutand cannot be fractionally condensed, althou h, the process may beadapted to step distillation, Which is multiple fractionating. Where theinvention is applied for the treatment of a mass of asphaltic liquid atrest, the process becomes an intermittent distillation, and as such, ismultiple fractionating. In carrying out the invention, it must beunderstood, that all fire gases are not applicable for such purpose, butonly such asf-show a-proper analysis suitable to the Work. to be done.Incase the required resultant product is air blown asphalt, then firegases showing from 5% to 10% of excess oxygen may be used to advantage,and which produces an asphalt having a large demand for special purposesbut the distillates resulting from the treatment are Worthless, exceptfor fuel, due to oxidation of the vapor which takes place.

Where the invention is employed for the manufacture of lubricatingdistillates or any other products which are to be treated oriltered,then the tire gases should be approximately free from oxygen,although, it is possible to carry a trace of carbon monoxid, though ifany large amount appears the re is likely to be yellow or smoky and willcontaminate the products with soot.

While no particular fuel nor form of generator are required, stillWhatever type 1s ,used must be capable of close regulation generatoremployed, but 1000 degrees F. at

the evaporator inlet may be taken as a safe maximum.

To obtain the necessary reduction 1n temperature we ma proceed in threeways, viz:

radiation, dilution or absorption.

Radiation into the air of the excess heat reduces the fuel eiiiciency tothat of a cylindrical still; and cannot be considered from an operatingstandpoint.

Dilution is simple, easy to c0ntrol,.reason ably eiiicient, and has thegreat advantage of increasing the volume of dry gas atmosphere. Eithercooled gas from the discharge of an apparatus, or wet steam, may beused. The latter shows a lower fuel eiiiciency, when the heat requiredfor evaporation of the water is included. Dilution by means of eithersteam or gas is the plan Vbest adapted to small installations.

Absorption of the excess heat in doing useful work raises the fueleiiiciency to a very high point, and either alone or in combina tionwith dilution is the plan best adapted to large installations. A.portion of the heat may be transferred to the entering oil, which maysafely and advantageously be preheated to a temperature suificient toevaporate any water, thus avoiding frothing or spattering in theevaporator. But approximately only to of the temperature drop may be soutilized,'and the balance must be absorbed in steam generation, or takencare of by dilution.

The vapors from whatever type of evaporator (continuous or intermittent)isuised should pass first to a scrubber. This may be a shell of roughlySi the cubic .capacity of the evaporator, in which the gas-vapor mixtureis sufficiently slowed down to allow theseparation of any coarseparticles of raw material which may have been accidentally carried over,and the scrubber must be insulated toprevent loss of heat by radiation,as any distillate condensed here has to be redis tilled.

The gas-vapor mixture should be cooled to condense the vapor, and thecondensate removed from the gas. Cooling is simple, and may beaccomplished in any type of condenser, air or water cooled. Itis highlyessential, however, to cool to the lowest possible temperature, if anyvolatile elements exist in the raw material, as because of the partialpressure of the gas, losses will result if the cooling stops at atemperature where any of the constituents of the condensate have anvapor pressure.

moval of the condensate from the gas is a more difficult matter, but wehave discovered a satisfactory method for accomplishing such removal,this being to centrifugel at a high velocity. A straight, or better, acurved vane centrifugal fan is highly suited vto this use, and may be soconnected as to provide for aspiration, and for returning the spent gasrequired formoderating fire gas temperature.

The point and manner of application of the centrifugal effect are ofimportance. If the distillates to be removed are relatively nonviscous,then the fan should be put at the end of the system, beyondthecondenser, as thus it handles a smaller volume, and cold gas only.But so located, if any very viscous distillates are run, they are quitelikely to emulsify in the condenser, and in that condition separate thewater of combustion very slowly. F or such oils the fan should be placedbetween the scrubber and the condenser, and sufiicient air coolingprovided between the scrubber and condenser to condensel the distillatebut not the water, leaving this to be taken care of by the condenser.

In either situation the effectiveness of the fan as 'a centrifuge ismuch increased by reducing the velocity of the gases just prior to entryinto the fan. This is accomplished by an enlargement of the vapor line,which also provides the necessary air condensing surface. rlhe reductionin velocity appears to allow time for the finer particles'to coalesce,

thus increasing their tendency to gravitate out of the gas.

rlhe essential .object of the present invention is, the treatment of theasphaltic liquid for the production of a single fractionation and thiswithout a previous cracking of the oil being resorted to in thetreatment of petroleum for the fractionation thereof and without thesplitting of the oil to be treated and the spraying of the same into avaporizing chamber.

Any suitable form of apparatus may be employed for carrying out themethod of treatment, but in the accompanying drawing, we have 'shown asimple'.y apparatus for use in connection with the invention.

Referring to the drawings, wherein is illustrated a longitudinalsectionalview of an apparatus designed for the carrying out of thepresent invention, the method will be readily understood by adescription thereof.

Gas or oil fuel under pressure, enters the burner 1, from the fuelsupply pipe 2, and the air under pressure or aspirated, as preferred, isadmitted by the pipe 3, to the said burner, the fire flame from theburner entering and filling the fireclay tube 4, which is controlledvalve 7, and after taking up such' heat as may be conducted through thefireclay wall enters the tube 4, at the bottom thereof, through thevents 8, the quantity of gas so admitted, into the tube 4, beingregulated or controlled by the valve 7, according to the temperaturedesired at the top of the tube 4.

The fire gases ejected from the tube 4 are conveyed by the pipe 9 intothe evaporator at a point adjacent the bottom thereof, while the raw oilor liquid hydrocarbon to be treated is admitted .under pumping pressureinto the upper end of the evaporator through the oil supply pipe 11, theoil or liquid to be treated discharging therefrom, onto the upper or topoil receiving plate or pan 12, there being a series of such plates orpans horizontally disposed within the evaporator 10. When the oildelivered onto the upper plate 12, completely fills the same, the excessoil overflows, and gravitates onto the next plate of the series ofplates and from this plate onto the one arranged there-below and so onthroughout the series of plates, it being understood that the plates arearranged in staggered and vertically disposed relation. The oil reachingand filling the bottom plate of the series of plates 12, overflows tothe bottom of the evaporator 10 whence it passes out through the trappedoutlet pipe 13. During the downfiow through the evaporator of thehydrocarbon liquid to be treated, the same encounters an upflowingstream of hot products of combustion, which is discharged from the tube4, into the evaporator adjacent the bottom portion thereof through thedischarge pipe 9, and passes upwardly through the evaporator to theupper end thereof and during the said upward How of the hot products ofcombustion, the same pass around and over the plates 12, arrangedtherein, heating the oil within the plates or pans and flowing over thesaid exposed surface thereof absorbing the vapors therefrom. The oil orliquid hydrocarbon as it flows downwardly over the plates 12, within theevaporator is progressively heated and evaporated and by properlyregulating the tempe'rature and quantity of the fire gas ad-V mittedinto the evaporator and the rate of oil feed of the oil or liquidhydrocarbon discharging into the evaporator, any desired degree ofdistillation and reduction may be produced. I

In the type of evaporator disclosed in the drawings, the oil supportingplates 12 are affixed to a vertical rod 14, which at its llower endrests on and is supported by a bracket 15 within the evaporator 10, andthe staggered arrangement of the plates 12 is such that they do nottouch or come in contact with the inner Wall surface of said evaporator.The rod 14, is removable from within the evaporator on the opening or removal of the cover plate 16, of the evaporator, so that when the plates12 have accumulated sufficient mineral sedimentto interfere with thefree flow of the oil or liquid hydrocarbon to be treated, the saidplates may be wlthdrawn by a removal of the rod 14, to which they areheld and a clean set of plates substituted therefor.

The mixture of gas and vapor produced within the evaporating chamberpass directly therefrom into the outlet pipe 17', leading from thedischarge outlet of the chamber and are conveyed thereby into thescrubber 18, flowing beneath the vertically disposedbaffle platev 19,located within the said scrubber and then flowing upwardly and escapingfrom within the scrubber through the outlet 19 into the uppermost of aseries of connected pipes 20. At its bottom the-scrubber is providedwith a trapped outlet, through which the residue and dirty oil depositedis withdrawn, and which oil so withdrawn may be returned to the feedpipe for the crude oil for redistillation. The velocity of the gasesescaping from the scrubber into the first of the series of pipes 20 issuitably reduced, due to the fact, that these pipes are of a greaterdiameter than that of the pipes 9 and 17, so that the temperature dropsby expansion to a sufficient de ee to reduce the vapor to the form of amlst, the water vapors however, not being condensed. This mist passesthrough, and in fact, is drawn through the series of pipes. 20, by meansof a centrifugal22, where the oil particles arek centrifuged out andflow in a stream under pressure together with the gas and water v teringthe chamber 24, through the inlet 25 and escaping therefrom through theoutlet 26, the condenser 23 being thus water jacketed. In thiscondenser, the ,water vapor is condensed `and any remaining traces ofoil are also liquefied, and the total distillate and water flowing' fromthe condenser through the trapped outlet pipe 27, while the cold gasesrise within the outlet pipe 28, provided for such gases, and escapesthrough the valve'controlled pipe 29, the outlet being regulated by thevalve 30, situated within said pipe.

It will be understood that the centrifugal fan 22 maintains a slightvacuum on the entire system back to the fireclay tube 4, the extent ofsaid vacuum being regulated by the valve 31, interposed within theconnection between the lowermost tube 2O and the centrifugal chamber22', the said fan also holding a slight pressure on the condenser 23,and the pipes 28 and 32, and whatever of the spent gas may be requiredfor controlling the temperature in the pipe 9 is taken from the pipe 32,the fiow of the same being regulated by the vvalve 7, interposed withinthe pipe 32, at or near the top of the annular chamber 6, surroundingthe shell 5 of the fireclay tube 4. The excess spent gas escapes throughthe valve controlled outlet 29.

As before stated, any suitable type of ap paratus may be employed forcarrying out the invention, but preference is given to such aconstruction as will permit of a continuous down flowing stream ofliquid hydrocarbon being subjected to the action of an ascending streamffow of hot products of combustion, which products of combustion Iarebrought in intimate contact with the fiowing mass of the liquidhydrocarbon so as to thoroughly heat the same and absorb the vaporstherefrom. An apparatus may be employed whereby the liquid hydrocarbonto -be treated is held and maintained at rest within a suitablereceptacle, and the hot combustion products brought into direct contactwith the exposed surfaceof the said liquid and by such flow actionheating the mass of liquid oil and absorbing therefrom the vapors, andfor this purpose, if so desired, the hot products of combustion may beforced upwardly through said mass of crude material.

' rl`he invention set forth resides in a single fractionation of theliquid hydrocarbon and this irrespective of the means employed, so longas the liquid hydrocarbon to be fractioned is not confined withinmetallic walls, through which walls the heat of the hot products ofcombustion is transferred, and the invention is more specificallydesigned for the production of lubricating oils, road oils and asphaltsand has no particular concern with'what subsequent treatment the sepa#rated volatile ed to.

By the use of the described invention, many advantages are realized overthe methods nowv employed for the fractionation of liquid hydrocarbons,and which may be termed, heat interchanging systems, for instance:deposition of carbon on metallic transferring surfaces, and thereforeover-heating and rapid depreciation is entirely obviated, deposits ofsoot, sediment or carbon due to the accidental over-heating may beconfined to removable surfaces, thus reducing time and labor of cleaningto a nominal figure; decomposition due to over-heating of even thetenderest sulfur crudes may be entirely overcome, and the portion of theapparatus employed containing the actual fire is much reduced in volume,making effective insulation or regenerative jacketing possible, and itis possible by the use of the present procportions of the oil issubjectess to obtain products which are not obtainable from the samematerial by the processes at present employed, and this applies todistillates and residues.

It will be noted that by the use of our.

process the raw material to be treated is not discharged into 'avaporizing chamber in the form of spray, but the raw material is actedupon, as a mass or sheet of oil, and as a matter of fact, everyprecaution is taken to prevent any portion of this sheet or mass frombeing accidentally detached and converted into a spray, inasmuch as theformation of a spray or an atomization of the-raw material would defeattheobject of the present process.

Having thus described the invention, 'what is claimed as new and desiredto be protected by Letters' Patent of the United States, is A 1. rlhemethod of producing a single fractionation of liquid hydro-carbonwithout tie-composition, which consists in subjecting the exposedsurface of masses of liquid hydro-carbon to the direct action ofhotproducts of combustion free from oxygen, reducing the temperature ofthe hot products of combustion and causing the same to flow over theliquid hydro-carbon in a counter direction to the fiow of said massesfor the heating thereof and absorbing the vapors therefrom.

2. The method of producing a single fractionation of liquidhydro-carbon. without heat decomposition which consists in generatingfire gases freefrom oxygen, reducing the temperature of these gases,subjecting the exposed surface of a conned flowing body of liquidhydrocarbon to the direct action of a counter-flowing stream of saidgases for the heating of the traveling flow of liquid hydrocarbon andabsorbing the vapors therefrom.

3. rThe method of producing a single fractionation of liquid hydrocarbonwithout heat decomposition, which consists in causing a stream of hotproducts of combustion freed from oxygen and reduced in temperature toow counter 'to a confined flowing body of liquid hydrocarbon to heat thesame and absorb th'e vapors therefrom, thence withdrawing the vapors andforcing the same throughi a condenser whereby the water and the oilcontained within the vapors are liquefied and separated.

4C. Illhe continuous method of producing a single fractionation ofliquid hydrocarbon without heat decomposition which consists in reducingthe temperature of hot products of combustion freed from oxygen,subjecting the exposed surface of a confined mass of liquid hydrocarbonto the direct action. of a stream of said products of combustion causedto flow equally over the mass of liquid hydrocarbon for the heating ofassures the liquid mam and absorbing the vapors therefrom, withdrawingthe said vapors and forcing the same through a condenser for theseparation of the water and the liquifying of any oil which may becontained within the vapors.

5. rlhe continuous method of producing a single fractionation of liquidhydrocarbon which consists in subjecting an exposed surface of a massof'liquid hydrocarbon to the direct action of hot products of combustioncaused to flow thereover for the heating of the liquid hydrocarbon andabsorbing the vapors therefrom, thence causing the vapors to be passedthrough a scrubber, thence withdrawing the vapor from the scrubbers andsubjecting the same in the form of a mist to a centrifugal for thecentrifuging of the oil particles therefrom, and thence forcing thesame, together with the gas and water conta-ined therein in and througha condenser.

6. The method of producing a single fractionation of liquid hydrocarbon,which consists in subjecting the exposed surface of an undivided body ofliquid hydrocarbon to the l direct action of a flowing body of hotproducts of combustion free from oxygen and re duced in temperature forabsorbing and removing the vapors therefrom.

7. rlhe continuous method of producing a single fractionation of liquidhydrocarbon, which consists in generating hot products of combustionfree from oxygen, reducing the temperature of these gases, subjectingall portions of an undivided confined body of liquid hydrocarbon equallyto the direct action of a flowing body of said temperature regulated hotproducts of combustion for removing from all portions of said liquid anequal and substantially predetermined proportion of volatile elements;forcing the. removed vapors through a condenser for a separation of thewater therefrom, and liquefying any oil which may be contained therein.

8. The method of producing a single fractionation of liquid hydrocarbonwhich consists in generating lire gases free Vfrom oxygen, reducing thetemperature of these gases, applying the gases to the exposed liquid tobe' treated whereby to heat all portions of the liquid substantiallyequally thereby removing from all portions a substantially equalproportion of volatile elements and whereby to avoid carrying over withthe generated vapors any material portions of non-volatile elements,cooling the mixture of spent gas and vapor to a temperature at which thevapors will be liquefied, and separating the condensed vapors from theaccompanying non-condensable gases. Y

9. The continuous method of producing a single fractionation of liquidhydrocarbon which consists in generating hot gases free from oxygen,reducing the temperature of these gases, applying the gases so reducedin temperature to the exposed surface of a mass of liquid hydrocarbonwhereby to heat all portions of the liquid substantially equally andthereby removing from all portions a substantially equal proportion ofvolatile elements, causing the vapors to pass through a scrubber,removing the vapors from the scrubber, and separating the condensedvapors from the accompanying noncondensable gases.

10. rlhe continuous method of producing a single fractionation of liquidhydrocarbon which consists in subjecting an exposed surface of a mass ofliquid hydrocarbon to the direct action of heated products of combustioncaused to flow thereover for the heating of the liquid hydrocarbon andabsorbing the vapors therefrom, subjecting the vapors to a coolingmedium and subjecting the same in the form of a mist to a centrifugalfor the centrifuging of the oil particles therefrom, and thence forcingthe same, together with the gas and water. contained therein in andthrough a condenser.

1l. The continuous method of producing a single fractionation of liquidhydrocarbon, which consists in subjecting an exposed surface of a massof liquid hydrocarbon to the direct action of hot products of combustionfreed from oxygen and reduced in temperature, said products being causedto flow over said liquid hydrocarbon for the heating of the same andabsorbing the vapors therefrom, thence causing the vapors to be 'passedthrough a scrubber, thence withdrawing the vapors from the scrubber and'subjecting the same in the form of a mist to a centrifugal for thecentrifuging of the oil particles therefrom.

'12. 'llhe continuous method of producing a single fractionation ofliquid hydrocarbon, which consists in generating fire gases free fromoxygen, reducing the temperature of these gases, subjecting an exposedsurface of a mass of liquid hydrocarbon to the direct action of saidgases, the temperature of which has been reduced but is still hot, saidgases being caused to flow over said exposed surface for the hea-ting ofthe liquid hydrocarbon and absorbing the vapors 4 PAUL PRUTZMAN. GUY L.GOODW'lN.

